Certain substituted 1-benzimidazole-carboxamides

ABSTRACT

THE INVENTION RELATES TO BENZIMIDAZOLYL DERIVATIVES OF THE GENERAL FORMULA   1-(R5-X-CO-),2-R4,R1,R2,R3-BENZIMIDAZOLE   WHEREIN R1, R2 AND R3 MAY BE IDENTICAL OR DIFFERENT AND EACH REPRESENTS HYDROGEN, HALOGEN, ALKYL, ALKOXY, ALKYLTHIO, ALKYLSO-, ALKYLSO2-, -NO2, -CN, CF3, CHO, COOR&#39;&#39;,   -CO-N(-R&#39;&#39;)-R&#34;, OR -SO2-N(-R&#39;&#39;)-R&#34;   WHEREIN R&#39;&#39; AND R&#34; EACH REPRESENTS HYDROGEN OR LOWER ALKYL AND R4 REPRESENTS HYDROGEN OR AN ALIPHATIC OR CYCLOALIPHATIC RESIDUE, X=O, S, -NH- OR N-ALKYL AND R5 REPRESENTS AN ALIPHATIC, ARALIPHATIC OR AROMATIC RESIDUE. THESE NEW COMPOUNDS ARE VERY EFFECTIVE AS INGREDIENTS IN BICIDAL PREPARATIONS FOR PLANT-PROTECTION AND COMBATING INSECTS, ACARIDES, NEMATODES, ENDOPARASITES AND MICROBES.

United States Patent Oflice 3,772,324 Patented Nov. 13, 1973 3,772,324 CERTAIN SUBSTlTUTEDl-BENZIMIDAZOLE- CARBOXAMIDES Stefan Janiak, Base], and Otto Rohr, Therwil, Switzerland, assignors to Ciba-Geigy AG No Drawing. Original application Oct. 22, 1968, Ser. No. 769,699, now Patent No. 3,652,580, dated Mar. 28, 1972. Divided and this application Dec. 2, 1971, Ser. No. 204,299 Claims priority, application Switzerland, Oct. 26, 1967, 15,005/67 Int. Cl. C07d 49/38 US. Cl. 260-309.2 3 Claims ABSTRACT OF THE DISCLOSURE The invention relates to benzimidazolyl derivatives of the general formula wherein R R and R may be identical or different and each represents hydrogen, halogen, alkyl, alkoxy, alkylthio, alkylSO-, alkylSO NO CN, CP CHO, COOR,

This application is a division of our application Ser. No. 769,699, filed Oct. 22, 1968, now US. Pat. No. 3,652,580, issued Mar. 28, 1972.

The present invention provides compounds of the general formula l-X-R wherein R R and R may be identical or different and each represents hydrogen, halogen, alkyl, alkoxy, alkylthio, alkylSO, alkylSO -NO CN, CF CHO, COOR',

CON or SOZN RH! RII wherein R and R" each represents hydrogen or lower alkyl, and R represents hydrogen, or an aliphatic or cycloaliphatic residue, X*=O, S, --Nl-I or N-alkyl and R represents an aliphatic, araliphatic or aromatic residue.

The present invention also provides a pesticidal preparation which comprises, as active ingredient, at least one compound of the general Formula I given above, together with a suitable carrier.

The preparation may contain one or more of the following additives: a solvent, a dilutent, an emulsifier, a dispersing agent, a thickener, an adhesive as well as other known pesticides.

The active substances defined by Formula I possess various interesting biocidal properties. They not only act as herbicides and defoliants, but at lower concentrations, at which no phytotoxic side effects arise, they show a strong lethal action on various representatives of the order acarina (ticks, spider mites and the like), insects and soil insects, their eggs and larvae, storage pests, for example cockroaches, snails and their eggs, nematodes, plant-pathogenic and human-pathogenic fungi, bacterial and viruses, animal-pathogenic and human pathogenic worms and spirochetes.

The symbol R in the general formula of this invention is defined as hydrogen or an aliphatic or cycloaliphatic residue. The aliphatic residue may be saturated or unsaturated and preferably represents a lower alkyl residue; it may furthermore be interrupted by O, S, SO, S0 and the like, and may optionally also contain cyano, carboxamido or carbalkoxy groups. Perhalogenated aliphatic residues are excluded by this definition. Possible cycloaliphatic residues are, above all, cycloalkyl residues for example, the cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl residue.

R in the general formula in this invention is defined as an aliphatic, araliphatic or aromatic residue; the aromatic residue, preferably phenyl, may be substituted in the most diverse manner, for example, by halogen atoms, or alkyl, alkoxy or alkylthio residues, or by the groups -NO CN, CF;, and the like. If R is an aliphatic residue, it may be interrupted by O or S, and preferably represents lower alkyl residues.

Examples of compounds in accordance with the invention, are compounds of formula:

R1 which have an especially good herbicidal action. In this formula R R and R have the significance mentioned above, with R and R preferably representing hydrogen, lower alkyl, halogen alkyl or N0 and R representing hydrogen, lower alkyl or cycloalkyl; R represents hydrogen or lower alkyl and R represents lower alkyl, phenyl, alkylphenyl or halogenalkylphenyh R1 R2 R4 R6 R7 H H H CH CH H H CH CH OH; H H Cyclopropyl H OH; H H Cyelopropyl CH CH H H C2115 H CH5 H H 02H, CH CH3 H H CaH1 H CH3 H H C3117 CH3 CH3 Cl H H CH3 CH: 01 H CH H CH3 Cl H CH CH CH Cl H Cyclopropyl H CH; Cl H Cyclopropyl CH; CH; 01 H 02H, H CH; 01 H 02H CH CH3 01 H C H H CH 01 H C H CH; CH; Cl H CH H 0 H, 01 Cl CH3 H CH; 01 Cl CH CH3 CH N02 H H CH CH NO: H CH3 CH CH N02 H Cyclopropyl H CH N02 H Cye1opropy1 CH CH TABLECntinued N07 H CzH H CH3 NO: H CzH5 CH3 CH5 N02 H C 117 H CH3 N 02 H C H1 CH3 CH3 N02 H CH3 H CaHs CFa H H CH CH3 CFa H CH CH3 C F3 H CH CH3 CH3 CF; H C2H5 CH3 CF3 H CgH5 CH3 CH3 CF; H C H7 H CH3 CF; H C5H7 CH3 CH3 CF; H CH3 H CnH CH3 H H CH3 CH3 CH H CH3 H CH3 CH3 H CH3 CH3 CH3 CH H Cyclopropyl H CH3 OH; H Cyclopropyl CH CH CH3 H CzH5 H CH3 CH3 H CzHs CH CH3 OH; H C H7 H CH CH3 H C3H7 CH CH3 CH3 H CH H C H5 The compounds, for example of formula N Br N O=C 0 R3 (III) are especially distinguished by their herbicidal, fungicidal and ovicidal action. -In this formula R R and R have the significance mentioned, with R R and R preferably having the definitions given for Formula H, and wherein R represents a lower alkyl, phenyl, halogenophenyl, nitrophenyl, lower alkylphenyl or benzyl residue.

H H H CoH5 H H H CaH4CHa(m) H H H OH;

H H CH OH:

H H CH C3117 Cl H H CeHaCl2(3,4)

Cl H H CeH4CH3(m) 01 H H C2 5 Cl H H 3 1 Cl H CH3 CsH Clz(3,4)

NO: H H ctrrtcmn N03 H H CzHg N02 H CH CH4CH (111) N02 H CH C111 OH; H H CoH4C a( CH; H H 2H5 CH3 H CH: a sC1z(3,4)

OH; H C CaH4CHa(rn) 3 H CzHs CF; H CH1 CoHaClz(3,4)

CF; H CH3 CaH7 NO: H Cyclopropyl 0 H OH, H Cyclopropyl (3 H,

N02 H Cyclopwpyl CH CH H Cyclopropyl CH Cl H Cyclopropyl CsHa 01 H Cyelopropyl C(LHSCIZ (3 4) 01 H Cyclopropyl CuH4CH36I1) Cl H Cyclopropyl CzH5 01 H Cyclopropyl C 111 (n) Cl H Cyclopropyl C;H1(i) Cl H Cyclopropyl C4Hn(n) Cl H Cyelopropyl Bcnzyl Cl Cl Cyclopropyl CH;

C1 C1 Cyclopropyl Benzyl The active substances of Formula I represent benzimidazolylurethanes, -thiolurethanes and -ureas.

They may be manufactured according to the methods usual for the preparation of this class of substances.

As a rule, the procedure followed is to react a benzimidazolyl derivative of formula R1 N R \CR4 A (IV) with a compound of formula wherein A and B are groups which are able to form the grouping (LX- ll whilst undergoing elimination or condensation.

In general, the procedure followed will be to react, in optional sequence, a reactive derivative of carbonic acid or thiocarbonic acid with an imidazole of Formula IV (A=H) and an amine of Formula V (B=NH or NH- alkyl) or an alcohol or phenol of Formula V (B=OH).

Industrially, the procedure followed for the formation of the ureas will be to react an imidazole of Formula IV (A=H) with an isocyanate or a carbamic acid chloride, whilst in the manufacture of urethanes an imidazole of Formula IV is reacted with the desired chlorocarbonate.

The new preparations can be applied in many different forms, for example, in the form of sprays, dusting powders and granules. They can also be worked directly into the soil, optionally together with fertilisers.

Possible materials for the manufacture of directly sprayable solutions of the compounds of general Formula I are, for example: mineral oil fractions of high to medium boiling range, for example, diesel oil or kerosene, coal tar oil and oils of vegetable or animal origin, as well as hydrocarbons, for example, alkylated naphthalenes, or tetrahydronaphthalene, optionally using xylene mixtures, cyclohexanols, ketones, and furthermore chlorinated hydrocarbons, for example, trichlorethane and tetrachlorethane, trichlorethylene or trichlorobenzenes and tetrachlorobenzenes. It is advantageous to use organic solvents having boiling points above C.

It is especially appropriate to prepare aqueous forms for application from emulsion concentrates, pastes or wettable spraying powders by adding water. Possible emulsifiers or dispersing agents are non-ionic products, for example, condensation products of aliphatic alcohols, amines or carboxylic acids having a long-chain hydro carbon residue of about 10 to 20 carbon atoms with ethylene oxide, for example, the condensation product of octadecyl alcohol and 25 to 30 mols of ethylene oxide or that of soya fatty acid and 30 mols of ethylene oxide or that of technical oleylamine and 15 mols of ethylene oxide or that of dodecylmercaptan and 12 mols of ethylene oxide. Amongst the anionic emulsifiers which may be employed, there may be mentioned: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids, or the sodium salt of a petroleum-sulphonic acid. Possible cationic dispersing agents that can be used are quaternary ammonium compounds, for example, cetyl pyridinium bromide or dihydroxyethylbenzyldodecylarmmonium chloride.

In order to manufacture dusting and scattering agents, it is possible to use, as solid carriers: talc, kaolin, bento nite, calcium carbonate, calcium phosphate, also charcoal,. cork powder, wood flour and other materialsoivegetablm origin. It is also advantageous to manufacture the preparations in a granular form. The various forms in which the preparations can be used may, in the usual manner, be provided with additions of substances which improve the distribution, adhesion rain resistance or penetrating power; as such substances fatty acids, resin, glue, casein or alginates may be mentioned.

The preparations according to the invention may be employed by themselves or together with usual pesticides, especially insecticides, acaricides, nematocides, bactericides or further fungicides and/or herbicides.

The following examples illustrate the invention:

EXAMPLE 1 (a) Urea type:

35.5 g. of benzimidazole, 350 ml. of acetonitrile and 150 ml. of dimethylforrnamide were initially introduced into a 3-necked sulphonation flask. The flask was externally cooled in ice and the stirred solution was mixed with 17.5 g. of methyl isocyanate at -5". The reaction mixture was thoroughly stirred for 5 hours and thereafter mixed with 50 g. of ice. The product crystallised in druses and was filtered oil? and dried.

Yield: 49.5 g.=94%

Melting point: 94-96 (Compound No. 1).

(b) Urethane type:

38.6 g. of 2-cyclopropyl-5 (6)-ch1orobenzimidazole are dissolved in 210 ml. of chloroform in a three-necked flask. After adding 5 g. of magnesium oxide and 70 ml. of water, 22 g. of methyl chloroformate are added drop by drop at -15" C., while stirring well. When the reaction has subsided, the mixture is stirred for a further /2 hour, after which the organic phase is separated ofi in a separating funnel, washed with 25 ml. of water and dried over sodium sulphate. The solvent is distilled oif, and the residue recrystallised from acetone/water. Melting point: 57-6l (compound No.2).

The following compounds were also manufactured in an analogous manner:

N Br Melting R4 Rs point, C.

CH3 GeHs 103-105 CH C H Cl2(3, 4) 124-127 CH CsH4CH (m) 115-117 CH CaHaNO-Ap) 153-157 CH Benzyl -81 CH C4Hg(n) 38-40 H @11 80-88 H CH3 -95 CH8 C5115 80-93 CH3 CH3 48-55 C3H1(n) CaHs 100-101 sH7(n) CaHrfi) Oil C3H (n) CH3 80-85 H C611 -105 H CH 119-125 CH3 CeHs 127-132 CH CH3 137-142 H 05H; Oil H CH Oil CH3 CaHs 90-99 CH CH Oil CH3 CH3 86-90 Cyclopropyl CsHs 87-88 Cyelopropyl H; 38-40 Cyclopropyl CH 57-61 0=C S Rs Melting R4 Rs point, C.

Cyclopropyl 05H Oil H 05H: 117-123 H CH; 80-84 EXAMPLE 2 EXAMPLE 3 Compound No. 10 was applied in the post-emergence process to the test plants listed below using an amount of 2 kg. of active substance/ha. The application took place 12 days after sowing the test plants, when these had developed 1 to 2 genuine leaves.

5 =plant no longer viable 9=plant killed.

EXAMPLE 4 The urethanes listed in Example 1 showed a good action against weeds in the pre-emergence and in the postemergence process.

The following results were achieved for compounds of R and R is hydrogen or lower alkyl; and R is lower Nos. 33 and 35: alkyl or trifiuoromethylphenyl.

Pre-emergence Post-emergence No.35 No. 33 No. 35 N0. 33

Plant 10 kg. 5 kg. kg. 5 kg. 5 kg. 2 kg. 5 kg. 2 kg.

9 s 7 5 5 4 5 2 9 0 9 7 5 3 s 4 9 9 9 9 9 9 9 9 9 9 s 9 9 9 9 N 0'rE.--1=no damage; 5=plant no longer viable; 9=plant completely dead.

EXAMPLE 5 2. The compound of the formula Compound No. 23 was tested for its action against pow- N dery mildew fungi. Courgette plants (Cucurbita pepo L.) were grown in a greenhouse and sprayed once prophy- C-CH: lactically with an aqueous broth of the compound containing increasing quantities of active substance. Two days N after the treatment, the plants were infected with spores omflcm of Erysiphe cichoracearum DC, and after 12-14 days the plants were rated as regards fungal attack. The compound of the formula Hereupon, a lower inhibitory concentration of 30 ppm. N of active substance was found. H36

What is claimed is: CH 1. A benzimidazole compound of the formula H N lO-NHCH R1 3 CR4 References Cited R1 30 Henry et al.: J. Amer. Chem. Soc., vol. 71, pp. 2297- H 1 Chemical Abstracts, seventh collective index, vols. 56-

wherein R is lower alkyl, trifiuoromethyl or nitro; each NATALIE TROUSOF, Prim y EXaminel' 

